Treatment of terpene alcohol-alkali metal bisulphite reaction products



Patented May 17, 1938 PATENT FFEQE TREATMENT OF TERPENE ALCOHOL-ALKA- LI METAL BISULPHITE. REACTION PROD- UCTS . Robert C. Palmer and Henry J. Warmuth, Pensacola, Fla., assignors to Newport Industries,

Inc., Pensacola, Fla.

ware

No Drawing.

6 Claims.

I good wetting and detergent properties.

More specifically this invention relates to the pyrolysis of terpene alcohol-alkali metal bisulphite reaction products to form new compounds having good wetting and detergent properties.

cyclic terpene alcohols such as geraneol, linalool, the terpineols and the like will react with alkali metal bisulphites such as for example, sodium or potassium acid sulphites. The reaction products obtained are water soluble and are believed to be alkali metal salts of the sulphonic acids of the terpene alcohols.

' It is also known that there terpene alcohols such as terpineols and the like possess strong wetting and detergent properties but have very low solubility in water and must be reduced to a colloidal state by means of soaps and the like to utilize these properties. It might be expected therefore that the water soluble reaction productsof the terpene alcohols and alkali metal bisulphites would have even better wetting and detergent properties than the terpene alcohols themselves. However, such reaction products possess practically none of these wetting and detergent properties.

We have now found that the Water soluble reaction products of terpene alcohols and alkali metal bisulphites readily undergo a fairly low temperature pyrolysis to yield new products which have excellent wetting and detergent properties especially in the presence of strong acids.

The new products are reddish brown viscous liquids, acidic in character, and can be neutralized with alkali metals to lemon yellow colored compounds. The new products have a slight terpene odor, nitrate readily, couple with diazotized amino compounds, react with solutions of salts of the heavymetals, are quantitatively precipitated by aluminum salts, and have good wetting and detergent qualities in the presence of strong acids. The wetting qualities of these new compounds in the presence of an alkali are somewhat poorer than in solutions having a pH value below 5. Nevertheless, the wetting properties of 50 these new compounds even in the presence of an alkali are much greater than the wetting properties of the original terpene alcohol-alkali metal bisulphite reaction products.

It is, then, an object of this invention to pre- 55 pare wetting and detergent agents from the re- It is known that unsaturated aliphatic or a corporation of Dela- Application August 24, 1936, Serial No. 97,658

action products of terpene alcohols and alkali metal bisulphites.

A further object of this invention is to convert terpene alcohol-alkali metal bisulphite reaction products into new compounds having good wetting and detergent properties.

A further object of this invention is to pyrolize terpene alcohol-alkali metal bisulphite reaction products.

A further object of this invention is to prepare wetting and detergent agents by pyrolysis of the reaction products of a terpene alcohol and an alkali metal bisulphite.

Other and further objects of this invention will become apparent to those skilled in the art from the following example and detailed description of a preferred form of the invention.

Preferred process of preparing terpene alcohol alkali metal bisulphite reaction products It is known that terpene alcohols such as, for example, alpha terpineol, will react with a dilute solution of sodium bisulphite in water if a large excess of the sodium bisulphite is used.

We prefer to prepare the reaction product, however, with an excess of the terpene alcohol present in the reaction mixture as follows: In any type of vessel, either open or closed, are charged 1500 parts of water, 100 parts of technical grade sodium bisulphite and 150 parts of alpha terpineol or a suitable mixture of solvents containing 150 parts of alpha terpineol, and/or other terpene alcohols. Steam distilled pine oil containing 50 to 60% or more of tertiary terpene alcohols is a suitable starting material.

The ingredients in the vessel are agitated at a temperature of 40 to 45 C. until a clear solution is obtained. Similar additional portions of reactants are then added to the vessel and the process is repeated. The process is repeated twice more by the addition of two separate portions of reacting ingredients. At the end of this time there are approximately 1000 parts of reaction product dissolved in 1500 parts of Water, plus unreacted alpha terpineol and/or other terpene alcohols which are now in solution, plus a small amount of unreacted sodium bisulphite and any impurities. The length of time of agitation for each batch of added ingredients is about two hours when a technical grade of sodium bisulphite is used. I

The contents of the vessel are then subjected to steam distillation and the greater portion of the excess terpineol and any other unreacted portions of the starting oil are recovered. When the concentration of the reaction product becomes from 55 to 60%, a precipitation of unreacted inorganic material results. The distillation is then stopped, the inorganic material filtered off and the remaining reaction product in solution is adjusted by the addition of water to a concentration of about 55% by weight. This gives a maximum concentration of product which will not tend to crystallize at room temperature.

The 55% solution of terpene alcohol-sodium bisulphite reaction products may then be used as the starting material for the preparation of the novel pyrolized compounds according to this invention.

Preparation of pyrol'ized terpineoZ-sodium bisulphite reaction products To 700 parts of terpineol-sodium bisulphite reaction products of about 55% concentration in Water are added 180 parts of 77% sulphuric acid. The mixture is heated gradually, preferably in a closed system, and as the heat increases, water is evolved as well as sulphur dioxide and a terpene hydrocarbon oil. The reaction is controlled by measuring the amount of water distilled from the boiling mass. When 140 parts of water have been distilled, the mixture in the still becomes cloudyand separates into two layers. The top layer contains practically all of the organic matter, some Water and sodium bisulphate. The bottom layer consists principally of water and sodium bisulphate with practically no organic matter. By the time 250 parts of water have been distilled off, a separation of these two layers should be made by drawing off the lower layer. The top layer is subjected to further heating until 45 additional parts of water have been distilled and the temperature in the liquid is about, but does not exceed 128 C.

A second separation of sodium bisulphate solution is made at this point and the top layer set aside for further processing.

It is preferred to make two separations of the water solution of sodium bisulphate because the amount of material to be separated reaches a maximum at the time 250 parts of water have been distilled off and thus a separation is made at this point in order to remove the greatest volume at one time. If the separation is attempted in one step at the end of the reaction, it is found that the control as evidenced by the amount of water distilled off is no longer a guide of the progress of the reaction. Furthermore, in this event, the final product is found to contain a larger amount of sodium bisulphate and requires more alkali to neutralize it, thus giving a poor quality product because of salt adulteration. At the end of the reaction as specified above there have been produced quantities of materials approximately as follows:

47 parts sulphur dioxide 32 parts terpene hydrocarbon oil 260 parts sodium bisulphate solution of which approximately 108 parts is sodium bisulphate and 152 parts is Water 250 parts of the desired final product containing approximately 63 parts of sodium bisulphate but practically no water 250 parts of water which has been distilled off during the reaction.

The sulphur dioxide produced may vary from 30 parts to 94 parts; the terpene hydrocarbon oil of the reaction product.

may vary from 26 parts to 56 parts; and the amount of water may be increased or decreased, but the amount of sodium bisulphate solution formed should remain relatively constant.

A variation of several factors, such as the strength of acid, concentration of terpineolsodium bisulphite reaction product, final temperature of the reaction and rate of distillation will change the approximate quantities of some of the materials produced by the reaction, but without great- 1y changing the most important property of the final product, viz., its wetting power. 7

The purpose of adding acid to the reaction product of the terpene alcohol and alkali metal bisulphite is to convert the reaction product into its acid form, since then the pyrolysis step proceeds smoothly to the desired final product. The pyrolysis does not proceed so satisfactorily if a free strong acid is present. Consequently, we use only sufficient sulphuric acid to form the acid salt, viz. sodium bisulphate. We have found that the acid salt is less soluble in the reaction mass than the neutral sulphate and therefore its formation enables us to obtain a product more nearly free from inorganic salts. If other acids, such as hydrochloric or phosphoric, were used in place of sulphuric acid, they should be used in amounts only sufficient to produce the corresponding alkali metal salts by combination with the alkali metal Preferably, no free strong acid is present in the reaction mass, but the scope of our invention does not exclude that possibility.

The use of very dilute acids is not so practical, since such use necessitates the evaporation of more water before it is possible to'reach the tem perature at atmospheric pressure where the pyrolysis reaction proceeds mo st therefore prefer to use a relatively concentrated mineral acid in the acidification step prior to pyrolysis.

The final temperature should not exceed 128 C. Higher temperatures cause rapid destruction of the product, converting it into water insoluble tar-like materials having little, if any, wetting power.

The product of the above reaction may be neutralized by any of the caustic alkalis or alkaline earth metal hydroxides, but sodium or'ammonium hydroxide is preferably used because the salts produced have a greater solubility in water.

In order to produce approximately a 60% water solution of the sodium salt of the product, there are added to 250 parts of the product obtained as described in the above example, 188 parts of 29 B. caustic soda solution (about 22% alkali)".

This yields a lemon yellow solution which can be readily handled and which is readily soluble in water. By the Clarkson-Draves wetting speed test, 0.35 part of this solution in 100 parts of water will wet in 25 seconds or less, in the presence of any strongly ionizable acid at 40 C. The amount of free acidity is relatively unimportant. Even of free sulphuric acid does not impair the efficiency of the wetting speed of the compound.

From the above description itshould be understood that this invention provides a method for the production of novel pyrolized products by acidifying and heating a terpene alcohol-alkali metal bisulphite reaction product. During 'this' heat treatment, sulphur dioxide, a-terpene hydrocarbon oil, sodium bisulphate solution, the novel pyrolized product and water are obtained.

The pyrolized product can be used as such as a wetting agent or detergent or can be conreadily. We

verted into a caustic alkali metal or an alkaline earth metal salt, which are also water soluble and form excellent wetting agents or detergent material. Both the pyrolized product and its water soluble alkali metal and alkaline earth metal salts are also good emulsifying and dispersing agents. For instance, a 60% concentration of the pyrolized product, or of any of its water soluble salts, in aqueous solution, enables the formation of clear solutions with ordinarily water immiscible liquids, such as vegetable oils, fatty acids, petroleum hydrocarbons, esters, ketones, terpene hydrocarbons, alcohols, natural resins, and the like. The clear solutions so formed, upon dilution with water, become stable emulsions or dispersions which may have a wide variety of uses.

The pyrolized product and its salts may, therefore, be used to advantage as emulsifying agents for water insoluble wetting agents like steam distilled pine oil, or terpineol, particularly so since it is possible to make both acid and alkaline emulsions that have stable characteristics. A large variety of other uses may be mentioned, including the use of the pyrolized product and its salts in the manufacture of lubricants, polishes, insecticides, emulsified coating compositions, cleaning and scouring compositions, waterproofing emulsions, and many others.

We are aware that numerous details of the process may be varied through a wide range without departing from the principles of this invention, and we, therefore, do not purpose limiting the patent granted hereon otherwise than necessitated by the prior art.

We claim as our invention:

1. The process of preparing wetting agents from terpene alcohol-alkali metal bisulphite reaction products which comprises heating the acid forms of said products at a temperature of not over 128 C. to distill oil water therefrom until the mixture separates into two layers, and recovering the top layer.

2. The process of converting a terpene alcoholalkali metal bisulphite reaction product into a wetting agent which comprises heating an aqueous solution of said reaction product at a temperature of not over 128 C. in the presence of sufficient acid to combine with the alkali metal of said reaction product to distill off water from the reacting mixture until the mixture separates into two layers, and recovering the top layer.

3. The process of preparing wetting agents which comprises preparing a mixture of an aqueous solution of a terpineol-alkali metal bisulphite reaction product and sufficient acid to combine with the alkali metal of said reaction product, heating said mixture to distill oil water from said mixture until the mixture separates into two layers, drawing oil the lower layer, subjecting the top layer to a further heat treatment to distill oif more water therefrom, permitting the mixture to separate again into two layers and recovering the top layer, the heating and distillation steps being carried out at a temperature not over 128 C.

4. The process of preparing wetting and detergent materials which comprises heating a mixture of 700 parts of a terpineol-sodium bisulphite reaction compound of about 55% concentration in water and the equivalent of about 180 parts of 77% sulphuric acid, allowing sulphur dioxide, a terpene hydrocarbon oil and water to be distilled from the mixture until the mixture separates into two layers, drawing off the bottom layer, further heating the top layer to distill off more water therefrom, allowing the mixture toseparate again into two layers and recovering the top layer containing the wetting and detergent material, the heating and distillation steps being carried out at a temperature not over 128 C.

5. The process of making wetting and detergent material which comprises heating together 700 parts of a 55% aqueous solution of a terpineol-sodium bisulphite reaction product and the equivalent of 180 parts of 77% sulphuric acid, distilling off 250 parts of water from the mixture at atmospheric pressure until the mixture separates into two layers, drawing off the lower layer, further heating the upper layer at atmospheric pressure to distill off 45 additional parts of water therefrom, again allowing the mixture to separate into two layers, and recovering the layer containing the pyrolized terpineol-sodium bisulphite reaction product.

6. The process according to claim in which the pyrolized product is reacted with an alkali hydroxide selected from the class consisting of alkali metal and alkaline earth metal hydroxides to produce a lemon yellow colored solution which is soluble in water;

ROBERT C. PALMER. HENRY J. WARMUTH. 

